1. BTC PTEC Biodiesel Workshop August 7 – 8, 2006 Session 3 – Feed stock and product quality

2. Agenda for third session Feed stock types Measurement of feed stock quality Biodiesel specifications Measurement of product quality

3. Feedstocks for biodiesel Vegetable oil –Soybean –Rapeseed –Palm Animal fats (lower cost) –Rendering plants Spent oils (lowest cost, so far) –Yellow and grey grease

4. Comparison of feedstocks Vegetable oil –Unrefined (high phospholipid content) un-degummed oils have separation problems in the process –Refined (better product) Animal fats –Lower cost –Higher concentrations of saturated FA –Biodiesel products may have higher freezing points –Higher cetane numbers

5. Comparison of feedstocks Spent oils –Trap grease (odor, moisture and color problems for this low cost feedstock) –Brown grease (FFA > 15%) –Yellow grease (FFA < 15%) –Cheaper

6. Vegetable oils US –Soybean oil (0.4 T oil/ha, 20% yield from seeds) –Canola and mustard oil (40% yield from seeds) Europe –Rapeseed oil (0.5 T/ha, 40% yield from seeds) –Sunflower oil (0.5 T/ha) Tropics –Palm oil (4 T/ha)

7. Feedstock preparation Removal of contaminants –Sediment < 2% –Moisture < 0.5 – 1% –Free fatty acids < 2 – 15% –Phosphatide and sulfur <20 ppm

8. Chemical quality Alcohols –Dry –Free of contaminants that may go into ester phase Catalysts –Dry

9. Fuel quality issues Free fatty acids Moisture (hard to keep out) Contaminants –Unreacted triacyl glycerols, alcohol –Unseparated glycerine –Mono and diglycerides Storage properties –Measure acid and viscosity to follow quality

10. Fuel contaminant problems Fuel filter plugging –From mono and di glycerides Engine deposits Fuel deterioration –Affected by presence of air, heat, metals –Biodiesel will absorb some water upon storage (1500 ppm) –May pick up material from storage tanks

11. Fuel standards US ASTM D6751 –Mostly same as for diesel fuel, except for –Acid number, glycerine –Higher limit on water Europe EN14214 (engine), EN14213 (heating) Diesel standard is ASTM 975 State standards for cloud point

12. ASTM D6751 Biodiesel Standard PropertyTestLimitsUnit Flash PointD93130 minDeg C Water and sedimentD27090.050 max% volume Kinematic viscosity @ 40 deg CD4451.9 – 6.0mm 2 /sec Sulfated ashD8740.020 max% mass SulfurD54530.0015 or 0.05 max% mass Copper strip corrosionD130No. 3 max Cetane numberD61347 min Cloud pointD2500reportDeg C Carbon residue (100% sample)D45300.050 max% mass Acid numberD6640.80 maxmg KOH/g Free/total glycerineD65840.02/0.24 max% mass PhosphorusD49510.001 max% mass Distil temperature (90% recovered) D1160360 maxDeg C

13. Comparison of diesel to biodiesel ASTM limits Property#2 DieselBiodieselUnit Flash Point52130 minDeg C Water and sediment0.050 max % volume Kinematic viscosity @ 40 deg C1.9 - 4.11.9 – 6.0mm 2 /sec Sulfated ash0.010 max0.020 max% mass Sulfur0.050 max0.0015 or 0.05 max% mass Copper strip corrosionNo. 3 max Cetane number40 min47 min Cloud pointregionalreportDeg C Carbon residue (100% sample)0.35 max0.050 max% mass Acid numberN/A0.80 maxmg KOH/g Free/total glycerineN/A0.02/0.24 max% mass PhosphorusN/A0.001 max% mass Distil temperature (90% recovered) 338 max360 maxDeg C Ash< 0.01% mass

14. Fuel related properties of diesel and methyl esters Diesel or Ester Cetane number Viscosity mm 2 /s 40 deg C Cloud point Deg C Pour point, Deg C Flash point, deg C ASTM limit47 min1.9 – 6.0report130 min Rapeseed48 - 534.5 - 5-3 to -6-9166 - 170 Soybean48 - 564 – 4.3-4 to 3-7 to 0130 - 240 Sunflower54 - 584.4 – 4.80 – 1.5-3 to 385 - 110 Tallow624.1 - 512 - 169 - 1396 - 190 Yellow grease 635.2 Grease6.25 Used fry oil594.51-3>110 No. 1 diesel482.6-50-5156 B20462.9-14-15

15. Analytical tests Gas chromatography (GC) –Ester identification and quantification Titration –FFA measurement – Iodine test Flashpoint (flammabilit) cup method Water and sediment (centrifuge for volume) –Low water solubility in biodiesel (15 ppm) Distillation (upper/lower limits for 90%) –Too low, may have to high a flashpoint –Too high, tendency of fuel to deposit on cylinder walls

16. Analytical tests Viscosity (falling ball or capillary method) Ash (muffle furnace method) Cloud point (temperature at which fuel first starts to crystallize), regional and seasonal Carbon residue (pyrolysis test) Glycerol (Gas Chromatograph) Acid number (potentiometric titration) Phosphorus (Inductively Coupled Plasma Atomic Emission Spectroscopy) Sulfur by Ultraviolet Fluorescence

17. Fuel properties Cetane number –Measure of ignition quality of fuel (autoignition property) –Hexadecane (cetane) has a cetane number of 100 –Biodiesel minimum of 47 (ASTM D6751) –Uses an engine (expensive)

18. Analysis and costs Full specification analysis –about $1300/sample –$1100/sample for seven consecutive samples (Magellan Midstream Partners Laboratory Service) Several analytical companies are equipped for analysis PerkinElmer offers on-line training courses

19. Fuel properties Cold weather properties –Cloud point Temperature at which fuel starts to crystallize –Pour point Temperature at which fuel cannot be freely poured –Cold filter plugging point (ASTM D6371) Lowest filtration temperature

20. Fuel properties Storage properties (oxidation) –Iodine value Indication of unsaturation of FA Indication of tendency to polymerize European limits of 120 (engine) and 130 (heating) –Rancimat test –Can improve with additives (same as for diesel fuel) or modification

21. National Biodiesel Accreditation Program Voluntary program for producers and markets to produce a standard biodiesel called BQ-9000 Includes ASTM 6751 standard and quality systems standards for the practices of: –Storage –Sampling and testing –Shipping and distribution –Fuels management Eight accredited producers in the US Market a BQ-9000 manual ($125)

22. Improvement of low temperature properties Additives (polymers) Winterization (cooling and filtration) –Results in loss of material and reduces CN Branched esters –Isopropyl ester has mp 6 - 7 deg below propyl –Higher cost